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111.
Ana Cristina Gmez-Herrero Carlos Snchez-Snchez Frdric Chrioux Jose Ignacio Martínez Jos Abad Luca Floreano Alberto Verdini Albano Cossaro Estelle Mazaleyrat Valrie Guisset Philippe David Simone Lisi Jos Angel Martín Gago Johann Coraux 《Chemical science》2021,12(6):2257
Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper. 相似文献
112.
The capacity for anaerobic decolorization of a sulfonated azo dye, Congo Red, by a strain of a sulfate-reducing bacterium
was evaluated. After optimizing the growth rate of the bacteria on a simple carbon source and terminal electron acceptor pair,
lactate and sulfate, respectively, the effect of the dye concentration on their growth rate was analyzed. The decolorization
rate was affected by the dye concentration in the growth medium. The azo-bond cleavage mechanism of reductive decolorization
with the formation of benzidine was consistent with the results, as this metabolite was identified by high-performance liquid
chromatography. Several fractions of the culture medium, including lysed cell extracts, were examined for the capacity to
reduce the azo dye. This reduction capacity was found in the culture medium in which the cells had previously grown. The results
showed that the mechanism of reductive decolorization of this sulfonated azo dye was extracellular and nonenzymatic, consistent
with the production of sulfide anion by the microorganisms while growing on lactate and sulfate. The sulfide anions were the
cause of the reduction leading to the disappearance of color in the medium. To increase the rate of decolorization, the presence
of ferrous ion was also necessary together with the lactate and sulfate substrates. 相似文献
113.
Fondo M García-Deibe AM Corbella M Ruiz E Tercero J Sanmartín J Bermejo MR 《Inorganic chemistry》2005,44(14):5011-5020
The new tetranuclear carbonate complex [Cu2L)2(CO3)] x 8H2O (1 x 8H2O) (H3L = (2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) has been obtained by two different synthetic routes and fully characterized. Recrystallization of 1 x 8H2O in methanol yields single crystals of {[(Cu2L)2(CO3)]}2 x 12H2O (1 x 6H2O), suitable for X-ray diffraction studies. The crystal structure of 1 x 6H2O shows two crystallographically different tetranuclear molecules in the asymmetric unit, 1a and 1b. Both molecules can be understood as self-assembled from two dinuclear [Cu2L]+ cations, joined by a mu4-eta(2):eta(1):eta(1) carbonate ligand. The copper atoms of each crystallographically different [(Cu2L)2(CO3)] molecule present miscellaneous coordination polyhedra: in both 1a and 1b, two metal centers are in square pyramidal environments, one displays a square planar chromophore and the other one has a geometry that can be considered as an intermediate between square pyramid and trigonal bipyramid. Magnetic studies reveal net intramolecular ferromagnetic coupling between the metal atoms. Density functional calculations allow the assignment of the different magnetic coupling constants and explain the unexpected ferromagnetic behavior, because of the presence of an unusual NCN bridging moiety and countercomplementarity of the phenoxo (or carbonate) and NCN bridges. 相似文献
114.
Fandos R Hernández C Otero A Rodríguez A Ruiz MJ Terreros P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(3):671-677
Titanium complexes with chelating alkoxide ligands [TiCp*(O(2)Bz)(OBzOH)] (1) and [TiCp*(Me)((OCH(2))(2)Py)] (2) were synthesised by reaction of [TiCp*Me(3)] (Cp*=eta(5)-C(5)Me(5)) with 2-hydroxybenzyl alcohol ((HO)(2)Bz) and 2,6-pyridinedimethanol ((HOCH(2))(2)Py), respectively. Complex 1 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) to yield the early-late heterobimetallic complexes [TiCp*(O(2)Bz)(2)M(cod)] [M=Rh (3), Ir (4)]. Carbon monoxide readily replaces the COD ligand in 3 to give the rhodium dicarbonyl derivative [TiCp*(O(2)Bz)(2)Rh(CO)(2)] (5). Compound 2 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) with protonolysis of a Tibond;Me bond to give [TiCp*((OCH(2))(2)Py)(mu-O)M(cod)] [M=Rh (6), Ir (7)]. The molecular structures of complexes 3, 5 and 7 were established by single-crystal X-ray diffraction studies. 相似文献
115.
Ana M. Gómez Aitor Barrio Serafín Valverde J. Cristóbal López 《Tetrahedron letters》2006,47(35):6243-6246
(Z)-exo-Glycals can be conveniently prepared in a convergent manner by Stille cross-coupling of (Z)-halo(Br,I)-exo-glycals and aryl or alkenyl stannanes, the latter are readily obtained by addition of tributylstannyl radicals to terminal alkynes. 相似文献
116.
The use of aerosol produced in a nebulization chamber is proposed as an alternative to gas sample capture in flow systems. This paper describes the coupling of a sampling interface with a flow system, for in situ gas monitoring. Aspects related with the behavior of aerosol formation and gas solubilization in liquid drops are discussed. The method is applied to the determination of residual lime in acidic soils. Aliquots of 5.0 ml of 1.0 mol l−1 HCl were mixed with soil samples (1 g). The CO2 released from these samples was captured by a nebulized aerosol and determined conductivity. The analytical curve from 1.0×10−2 to 5.0×10−2 mol kg−1 CaCO3 was ploted applying the matrix matching approach. This proposition, allowed an increase in the sensibility with detection limit of 6.0×10−3 mol kg−1. The precision was good (R.S.D. <3%) for an analytical frequency of 22 determinations per hour. A fair agreement, at 95% confidence level, was found between the results from the proposed method and certified values of the investigated samples. 相似文献
117.
1,2,4-Thiadiazolo[2,3-a]pyridinium chlorides undergo a very facile base promoted transformation to give bispyridilimino-1,2,4-thiadiazolidines. The unequivocal structural assignment of these last compounds was achieved by spectroscopic 1H, 13C and 15N two dimensional methods. 相似文献
118.
Ribeiro da Silva MA Gomes JR Ferreira AI 《The journal of physical chemistry. B》2005,109(27):13356-13362
The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-, 3-, and 4-chloroaniline were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of vaporization or sublimation of the three isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the three isomers of chloroaniline, in the gaseous phase, at T = 298.15 K, as 53.4 +/- 3.1 kJ.mol(-1) for 2-chloroaniline, 53.0 +/- 2.8 kJ.mol(-1) for 3-chloroaniline, and 59.7 +/- 2.3 kJ.mol(-1) for 4-chloroaniline. These values, which correct previously published data, were used to test the computational methodologies used. Therewith, gas-phase acidities, proton affinities, electron donor capacities, and N-H bond dissociation enthalpies were calculated and found to compare well with available experimental data for these parameters. 相似文献
119.
The protonation of five representative oxaziridines is reported for inert solvents (deuterio-chloroform or carbon tetrachloride) where conjugate acid formation may be effected by the addition of about 20% (v/v) TFA. Comparison of the 1H nmr chemical shifts for neutral and conjugate acid forms suggests that oxaziridines usually undergo protonation on the N-atom under these conditions. For one compound studied, 2-ethyl-3-p-nitrophenyloxaziridine, there is a possibility that protonation occurs on the alternative O-atom. The relevance of these findings to the mechanism of the acid-catalysed hydrolysis of oxaziridines is discussed. 相似文献
120.